Disazo pyrazolone dyes



Patented July 26, 19479 DISAZO PYRAZOLONE DYES Georges .Kopp, Mont Saint- Aignan, and Rene Gangneux, Rouen, France, assignors t Societe tion of France 'Anonyme de Matieres Colorantes et Produits @himiques Francolcr, Paris, France, a corpora- No Drawing. Application June 25, 1945, Serial No. 601,542. In France January 13, 1944 Section 1, Public Law 690, August 8, 1946 Patent expires January 13, 1964 4 Claims.

It is well known that the acylacetylated derivatives of the aromatic amines can be used for the preparation of acid azo dystuifs; however their use is usally limited to the production of yellow shades, which considerably restrains their use.

Now, we have found that one obtains valuable acid polyazo dyestuffs by using as intermediary coupling agents, instead of the primary amines which couple in para'position, products of the following general formula:

R--C 0 onto ONHONHz l IOi:

in which the benzenic nucleus as shown may contain other substituents such as the halogen atoms,

the alkoyl or :alkoxy groups and in which It represents a hydrocarbon radical.

The so obtained new dyestuffs answer the following formula:

(II) o o-ni following manner: one couples diazo compounds of aromatic amines or of amines behaving in diazotization like aromatic amines, and containing at least one group SOsI-I with products corresponding to the first formula. Thus, monoazo products of the following general formula are obtained a the said dyestuifs being diazotized and coupled with any coupling agents.

As initial diazotizable components one can use the amines of the benzenic, naphthalenic or amino-azo series, certain heterocyclic amines, all the said amines containing at least one group $0321 and being .contingently substituted by the halogen atoms or other groups or functions such as alkyl, alkoXy, CO2HCON -SO2N 01-1 or the like.

As final coupling agents capable of being used according to the present invention one can quote by way of examples: the betadiketones, the arylides of acylacetic acids, pyrazolones, benzenic or naphthalenic amines, phenols or napththols, diphenols, aminophenols, aromatic diamines, aminonaphthols, as well as the monoazo dyestuffs capable of coupling; all these coupling agents may be substituted or not by halogen atoms, groups of functions such as alkyl, alkoxy, SOsH, SO2N COzH, COH and the like.

The initial component of the dyestuir and the final coupling agent should contain a total of at least two groups 803K or at least one group SOsH and one function SOzNHz.

The middle or intermediary coupling agents can be obtained according to the method described in the Kopp et al. patent application, filed on June 25, 1945', Serial No. 601,541, now abandoned, for a Method for the preparation of mono-acylacetylated derivatives and products resulting therefrom, which consists in condensing with an acylacetic acid ester an amine of the following general formula:

the said amine contingently containing other substituents fixed on the benzenic nucleus such as the halogen atoms, the alkyl or alkoxy groups.

The dyestuiis according to the invention, the shades of which go from reddish yellow to green over orange, red, violet and brown, dye animal or anlmalized fibres; they possess excellent general fastnesses, preserve the cellulosic fibres perfectly and dye natural silk to the same height as wool.

Among the said dyestuffs the orange and brown ones are of interest because they make it possible tofill gaps in the scale of acid azo dystuffs.

Example 1 1'73 parts of sulphanilicaeid are diazot-ized in the usual manner and the solution of the 'diazo is poured rapidly into a s'olutionobtained by dissolving 237 parts of 4-arnino-3-nitro-acetoacetanilide (prepared as described hereafter) in 3,000 parts of icy water by means of 115 parts of caustic soda of 35' Be. a'ndjby adding 300 parts of crystallized acetate of soda.' The coupling is rather rapid and the resulting dyestuif;

which is colloidal at first, becomes rapidly crystalline. When the coupling has come to an end the formation is rendered acid through an addition of hydrochloricacid. 200 parts of hydrochloric acid of 19 Re. are still added and one diazotizes by pouring during about half an hour 138 parts or" sodium nitrite in solution at 50%. The diazotiz'ation is rapid and the diazo derivative precipitates in totality. The so obtained azodiazo compo'undis poured rapidly into a solution containing 2885 parts of 1'(2-chloro-5- sulpho) phenyl43 methyI-E-pyraZOlOne, 3,000 parts of icy water, 115 parts of caustic soda of 35 Be. and 450 parts of crystallized acetate of soda.

The resulting dyestufr, isolated in the usual manner, dyes 'a'ni'rnal fibres in yellowish orange which is very fastto light: This dyestuff has for its form'ula:

U G' C-Ha sole The preparation er the e-a'mino-e-nitrmacemacetanilide is infected as follows: o

153 arts or fiitro-paraphenylene-diarnine, 500 parts of monochlorobenz'ehe and 200 parts of freshly distilled acet'oacetate or ethyl are heated during two hours to a soft ebullition While re- 'inoving through distillation the alcohol which has formed in the course of the reaction. After a cooling of 24 hours the layer of the solvent is separated from the half-tarry and half-crystalline product which deposits. This precipitate is taken again in 1900 parts of boiling acetic acid of 40%. parts of -carboraffine are added; one filters and allows to crystalline through cooling.

Example 2 253 parts of ani-i-ine 2 fi -disulphbnic acid are diazoti'zed and the obtained diazo derivative is poured into a solution *of 4-arnino-3-nitro-acetoacetanilide identical with that of Example 1. The coupling being *compl'e'te, 'one acidifies through an addition of hydrochloric acid of 19 B. and further adds 200 parts of hydrochloric acid of 19 Be. One diazotizes by pouring in half an hour 138 parts of sodium nitrite in solution at 50%. The diazo compound which is first entirely in solution crystallizes partially. It is poured rapidly into a solution obtained by dissolving 177 parts of acetoacetanilide into 3,000 parts of Water by means of parts of caustic soda and by adding 450 parts of sodium acetate.

The resulting dyestufi dyes animal fibres in yellow with an excellent iastness to light. This dyestuff has for its formula:

Example 3 nitrite in solution at {50%. The azodiazo cornpound is poured rapidly into a solution obtained by dissolving 1'74 parts of 1-phenyl-3-methyl-5- pyrazolone in 3,000 parts of icy water by means of '715 parts of caustic soda'of 35 B. and by adding 450 parts of crystallized sodium acetate. The dyestuff, isolated in. the usual manner, dyes animal fibres in orange very fast to light. This dyestuff has for its formula:

cow-12a Examples itt.

CO-OHB CO-NHQ-NeN- 2,477,487 5 6 Example 5 yellowish orange shades and having the general In Example 4 the Neville-Winter acid is substituted by 315 parts of 2-phenylamino-8-oxynaphthalene-fi-sulphonic acid. The dyestufi, isolated in the usual manner dyes animal fibres 5 X =NO in yellowish brown very fast to washing, to fuller, to sulphur and to sweat. This dyestufi has for its formula: I

Example 6 In Example 4 the Neville-Winter acid is substituted by 512 parts of the dyestufi obtained by wherein X represents the radical of a diazotized coupling the diazo derivative of the paranitranibenzenic amine, carrying at least one SO3H group, line with the H acid in an acid medium. The Y represents the radical of a sulfonated derivaresulting dyestuff dyes animal fibres in a pure tive of a pyrazolone and R represents an alkyl green of good fastness. This dyestufi" has for its radical.

formula: 4. The disazo dyestufi for dyeing animal fibers 00-0113 G g on NH: 80811 N=NC\ c o-1\n1 N=N N=N-ONO 1 NO: 5on1 --SOIH What we claim is: in yellowish orange shades and having the 1. The method of preparing disazodyestuffs for formula: dyeing animal fibers in yellowish orange shades, 0043113 which consists in coupling a diazotized benzenic amine carrying at least one SOaH group with an O acylacetylated derivative of the general formula: 00NH N=N-0--o-om o2 HOG\N/N R-C 0 GHr-O ONH NH:

soda in which R represents an alkyl radical, diazotiz- GEORGES KOPP. ing the aminoazo compound obtained, and cou- E E GANGNEUX, pling the diazo-compound thus obtained with a sulfonated derivative of pyrazolone. 1 REFERENCES CITED 2. The method of preparing disazodyestufis for Th f dyeing animal fibers in yellowish orange shades, fi e ouowmg references are of record in the which consists in coupling a diazotized benzenic 1e of this patent amine carrying at least one S O3H group with UNITED STATES PATENTS g; fazleglaated benzenic derivative of the follow- Number Name Date 1,594,865 Zitscher Aug. 3, 1926 1,982,332 Taube Nov. 27, 1934 2,100,378 Carr Nov. 30, 1937 QHPMCHPGONHQNH 2,230,696 Petersen Feb. 4, 1941 N0: FOREIGN PATENTS Number Country Date diazotizing the aminoazo compound obtained, 393,267 Germany Mar. 31, 1924 and coupling the diazo compound thus obtained with 1-(2'-chloro-5'-sulpho) phenyl-3-methyl-5- OTHER REFERENCES pyrazolone. Georgievics and Grandmougin, Textbook of 3. A disazodyestufl for dyeing animal fibers in Dye Chemistry, pages 7, 94 (1920). 

